Photographic composition containing antiplumming and antibronzing agents



United States Patent" C 6 Claims. (GI.95t7)i This invention relates to photography 'and-moreparticularly to radiation-sensitive photographic elements in: cluding films,- plates and" papers. More particularly it relates-tophotographic'silverhalideemulsions and emulsion layers that contain (a) 4 achemicalagent 'lWhiCh" -im'- phves" the colorand densityof developed silver images and (b)- a--polymericamino nitrogen' containing, material. Stillmore particularlyit relates to such elements that have at least one photographicsilver 'h'ali'cleemulsion layer which has dispersedtherein. a small .amount of 1-) a finely divided. compound which prevents plumming""andz fbronzingi of {the develio'ped'imagesand (2') a'--polymeric, aminonitrogen containing'material soluble in dilute; aqueousaeetidracid butiinsoluble in watertand dilute" alliali'e's: A'- preferred aspect' of the invention relates to photographic elements having at leastone silver halide emulsion layerithat has dispersed therethrough-particlesmfsuch a polymeric, amino-nitrogen containing material whichlpartilclescontain a compound which..prevents plummingf ort bronzing of developed silver imagesw Theinvention also'relates to a method of making photographic silver halide emulsions and emulsion layers embodying such materials and compounds.

An'object of th is'Jinvent-ion is ,to provide photographic elements avith improved characteristics. Another. object is to 'provide photographicielements with silverhalide emulsion: layers that are resistant. to plumming or. bronzing during the hot glazing of developed photographic silver images. A -fiirther object is to--provide a more effective; method of= introducing and mainta ining anti-plumming or 'anti bronz-ing compounds: in photograpliic'silver halide "emulsion layersa Still other 'objeets will be -apparent :frorn the following description \of the invention. 7

The above and other obiects are attained and new and useful photographic silver halide emulsions and emulsions layers tal'fil obtained v.by incorporating, with'the emulsionst (1 as chemica-lt compoundsor agent which images,-. er g -iana-anti-Iplumming or antifbronzing-agent and 21) --a polymeric; amino-nitrogen. containing material hich :is. solubleindiliite aqueous; acetic acid: but in solubleninswater and dilute alkalies The latter material apparently 'hasaprotective .action on 'the compoundthat improvesuthe. colortondensity ofithet-silver images and prevents... said .compound from. beingwashed out ofis'the emulsionmlayers duringa photographic tdevelopinghop oration. However,.-'when.the:develooed1element-t is treats edtiriranacidmtopbathioran acid-rfi'itingrbathlthe. poly mericLamino-nitrogen containing mate'riallis' dissolved thus 'rele'asingjthe compound so. that 'it" becomes effective during -subsequentdryiu'g' of "the photographic "element and-prevents or'reducesiplumming' or bronzin'gi.

A practical method ofmakin'g the"improve'd"'photographic emulsions and emulsion layers comprises dissolvingsthe anti-plummingor anti-bronzingagent in ya waterimmiscible organic solvfent and .adding; the polymeric amino-nitrogen containing materialsormixing a solution 'of. i1the'-.. agent. with ai-solution of-ifithe polymeric aminonitrogen compound and then adding the resulting solution of the two materials to an aqueous solution or dispersion of a' water-permeable colloid or. an aqueousvcolloid silver-halide emulsion. The resulting coll'oidal'.i-.disper-v sion co'ntains finely divided particles ofthe="polymeric :aminonit-rogen-.containing-material which-particlescom improves 1116:2016! .--and.'.density of the. developed silver I "ice Ifllllszthe ztanti-plumming or =anti+bronzing compounds. ,In somecasesdhe antiv-plumming or: anti-.bronzing; agents which are of tan extremely; small; size 1 may be entirely surroundedtb-y a coating of" the polymeric amino-nitrogen containingmateriah t Thep'reparationtof-the particles 05 the polymericaminonitrogen containing; -.rnaterial-= which contains the antiplumming; or anti-bronzing'; agent tissnotlimited. tov the solution methods .-just described :but.can bevaccomplished in" other manners; for example; byvgrindingsthe anti-plumming ort anti-bronzing agentin-ra solution of: the polymerio amino-nitrogen containingmateri-al. High speed stirrers,- homogenizers s orcolloid mills may' be used advantageously: to assist the dispersiont of thew-agents in theamino-nitrogen:containing materialt- Theaparticle 'sizesofthe polymeric aminosnitrogenscon taining materialswhich contain r theanti-plumming v or antiabronzingaagent'rmays varyv over a fairlyywido-range, but, in general, ..shouldnot tbe\ greater than approximately? 30-. microns; The minimum size-is oot-critical and I generally 'is controlled-by; the-smallest molecular volume of-tthe particular amino-nitrogen containing; material in questiont- In dispersing, -tl1etpa1'ticlessinsthe, v (water-permeable col.- loid solutions, it is generally advisable to employ a wettingzzor dispersing Iag'ent; e: tgz scetyl trimetliylammonium bromide, sodium dodecylsulfate, sorbitan monolaurate, sorbitanztriblate containing at" least 20 oxyethylene groups at least three-chain's ';and\ other'ihexitan 1 derivatives such asr'those .described im 'Blake et'falt U. 81' Patent 2,400532}: tthef poly'oxyethylene ether 'ofdodecyl' alcohol, etc. i

The polymeric amino-nitrogen containing materials which. areusieftil inv accordance the invention 'form hardfresin like -film's." They-areinsoluble in' water and 51% a ueous ammonia; but'are' soluble in aqueous acetic acid of some concentration within. the range l to 5%. 'Iliose"so1uble-'i n11%" acetic'a'cid are preferred. Useful polymeric amino-nitrogen containin'gmm'aterialss-mayibe divided inrsevejral groups asifol'lowsz 1.: Those whichun'ayi be terrned 'celluloseaderivatives. This includes jdeacety'lateid," chitin and the valkylamino and famino-"alkylcelluloses.

2;Tl1'ose-which may'ibe classified as 'isynthetic resins in the"for.rn'ationof "which farnimonia' in some instances and monomeric-amino=nitrogen containing'j'bodies" other instances have been" employed, This group: is distinct from groupfl in "th'atthe highly polymeric molecules are built up::"who11 -"by synthesesf Among fjthesemate'ri'als are the resinous polymericfantino=alcohol esters. of "acrylic acid or of itshomolog's substitutedg' in'the"alphaposi tion by" a'ihy drocarbon radical: 'j the resinous reaction products 'of phenols alde'hydesand ammonia or primary or secondary amines, for example, the reaction product of 'meta-cresol, formaldehyde and dimethylamine; poly diii'ietl'iylamiriostyrene and the polymerization product of th'e -*olefiiiic compound" made by simple pyrolysis of p a acetoxy#ethylbenzyldimethyl ammonium acetate; etc.

3I"Tl1'ose'whi'ch may be termed protein derivatives and contain sufiicient amino-nitrogen groups toy enableithem tp; meet the-solubility requirements" of the definition given a ove;

suitable specifi'compounds mf the above" types are described in USS. P: 2,182,814 and-the various 'paten'ts which are'freferred to on' pages-"4"and Sof' th'atrpatent. One "of theiprefrred' polymeric amino-nitrogen contain ing* materials iS"' polymeric diethyla'minoethyl" methacrylate: Itcantbe -made 'fromf'methyl methacrylate and diethylaminoethanol' and subsequent" polymerization in accordance with the following -procedures: PROQEDURE' A r- PREPARAH-ION OF:-'MONOMER The 'followingcompounds "are admixed in" the amounts b'yyweight' given in the following'table in" a reaction .v'essel providedwitlf'a-packed distillation column in the outlet? Parts Diethylaminoeth-anoL--FMMMWM.ccnwpu-s-fi..117 Methyl methacrylate ..r Benzene/ 1712 Patented Dec. 14, 1954 This mixture is dehydrated by distilling ofi a benzenewater azeotrope from 69 C. to 80 C. One fourth (0.016% sodium based on the weight of methyl methacrylate) of the total amount of sodium methylate catalyst dissolved in methanol is added cautiously to prevent sudden flooding of the packed column. The reaction usually starts upon the cautious addition of a second equal quantity of catalyst. The methanol-benzene azeotrope is distilled off at approximately 59 C. as rapidly as possible to minimize side reactions. Dehydrated benzene is added continuously to replace that which is removed in the azeotropic mixture. Additional 0.016% catalyst increments are introduced at a rate sufficient to maintain a steady removal of methanol, as indicated by a constant head temperature of 59 C. at a moderate reflux ratio. The fourth increment of the catalyst causes the final 25% of total reaction, but the rate of methanol formation is very slow. When the reaction is complete, the catalyst is neutralized with the theoretical amount of acetic acid, and the monomer distilled off at 89-91" C. under a pressure of 10 mm. of mercury. Purity of the product is indicated by determination of the neutralization equivalent and refractive index. Since the monomeric diethylaminoethyl methacrylate thus obtained polymerizes readily on standing, storage time should be held to a minimum, preferably under 8 hours. Dilution with xylene and low temperature setorage are effective short term measures for restraining polymerization.

PROCEDURE B.-PREPARATION OF POLYMER A polymer-free solution composed of 50 parts by weight of monomeric diethylaminoethyl methacrylate in 40 parts by weight of xylene is heated to a polymerization temperature of 70-80 C. and 1.0%, based on the weight of the monomer, of azobisisobutyronitrile added as a polymerization catalyst or initiator. The molecular weight, and therefore the viscosity, of the polymer may be controlled by regulating the polymerization temperature. Because of more favorable solubility characteristics, toluene is used as the carrier for the initiator. For reaction times of 4 to 8 hours, 50% polymer solutions may be produced with viscosities of 2.0-3.7 poise containing less than of the original monomer unpolyrnerized. Control of a peak temperature, which occurs from 5 to minutes after adding the initiator, appears Example I A solution was prepared, containing 0.1 g. of l-phenyl- S-mercaptotetrazole as an anti-plumming agent dissolved in 12.5 ml. of ethyl alcohol containing methyl alcohol in the proportions, 100 parts 190 proof ethyl alcohol to 10 parts pure methyl alcohol. This was added to a solution which consisted of 5 g. of the diethylaminoethyl methacrylate polymer described in the above procedure B (48% polymer in toluene) dissolved in said alcohol mixture. The resultant solution was then dispersed in 150 ml. of distilled water containing 0.25 g. of dissolved cetyl trimethyl ammonium bromide, and the mixture was vigorously agitated in a blending mixer. The blending was continued for approximately three minutes after the initial mixing of the ingredients. The dispersion secured dilluted with distilled water to a total volume of A chloro-bromide emulsion (AgCl=95.2 mole per r Water ml 500 N-rnethyl-p-aminophenol sulfate g 3.0 Sodium sulfite (anhydrous) g 45.0 Hydroquinone g 12.0 Sodium carbonate (anhydrous) g 67.5 Potassium bromide g 1.9

Add water to make 1.0 liter.

with 2 parts of water, rinsed in water and fixed in a fixing bath of the composition:

Water ml 850 Sodium thiosulfate g 240.0 Sodium sulfite (anhydrous) g 15.0 Acetic acid (28%) ml 48.0 Boric acid (crystals) g 7.5 Potassium alum g 15.0

Add water to make 1.0 liter.

for five minutes followed by washing for an hour in running water at room temperature. Processed prints from each coating were dried on a hot ferrotype plate, a cold ferrotype plate and on a cheese-cloth type screen to evaluate plumming. The results are tabulated as fol-.

ows:

TABLE I li l R1 6 t eny -5- e atlve on rast Emulsion memwtm Fog Exposure Grade Plummed? tetrazole Control none none 2 Yes. With agent 1.360 none 30 2% No. With agent and polymer 0.400 none 25 2 Slight.

The last column of the table indicates whether or not plumming occurred on the hot ferrotype plate. The amount of 1-phenyl-5-mercaptotetrazole used in per emulsion unit which is defined as that quantity of emulsion having a silver content equivalent to that of 500 ml. of 3N AgNO3 at 25 C.

Example 11 To a solution containing 5 g. of the diethylaminoethyl methacrylate polymer described in procedure B above (48% polymer by weight in toluene) dissolved in 25 ml. of toluene was added slowly with agitation a solution prepared by dissolving 0.4 g. of l-phenyl-S-mercaptotetrazole in 10 ml. of ethyl alcohol containing methyl alcohol in the proportion, parts of 190 proof ethyl alcohol to 10 parts of pure methyl alcohol. The result ing solution was then dispersed in ml. of water containing 0.8 g. of sodium dodecyl sulfate free from electrolytes as the dispersant. Again a blending mixer was employed to aid dispersion, agitation being continued for three minutes after mixing the solutions. After blending, the suspension was diluted to 500 ml. with distilled water. The dispersion thus obtained was tested in the same manner as described in Example I. A summary of the significant results is presented in Table II:

Mer captoi tetrazdle 1* Emulsion- 'of .blen'din'g,.thesnspension wasldiliit'e distilled :water. They-resultant disperslo "the 'same manner 'as' described in Eiia'mple-l A tion of pertinent results .-is.givenin-Table IfL column of this table-iindicat'eslwhether ot-not:pliifnniing occurred on .a .hot .fer'rotype .plate.-

, 1 ably lme'tliylamiilofifefiiyl hyl ates "when 'slo'wlywith' agitatioma-solutioh*prepared by-dissolving H M I 0.5 g. of 1-phenylaSmrercaptotetragoleuin ml. of ethyl gg f gg i i 'gg ggg gag225 331 f 1!? f alcohol containing methyl alcoholfin the proportions,

" v Ms 3 m I ammoethanoL-in.equivalent:amount fonthediethylamino- Among the useful solvents or diluerit's which may be persed in 150 ml. of distilled water containing 2 g. of the sorbitan trioleate polyoxyalkylene ether described in Exus ed as a medmm for addmg the .antl Plummmg or m am le III free from electrolytes as the dispersant A blonzl-ng agent and Polymelzlc amm9'mtrogen contammg P material to the colloid solution or dlspersion are toluene,

blending mixer was used to aid dispersion, agitation being carried out for three minutes after mixing the solutions. gfigi gg g fg g z g g .353 2 3 32 3 32% Upon completion of blending, the suspenslon was diluted solvents to 500 ml. with distilled water. The dispersion obtained was evaluated in the same manner described in Example wlhfle gelatma been g g m-the fgre-gomg I The results are summarized in Table IV. The last es as Smta- 6 601101 or the sllvqr .ahde emul' c'olumn of this table indicates whether or not plumming sions other collolds can be substituted in llke manner occurred on a hot ferret 6 late with similar results. Among such colloids are poly- W p glycuronic acid, polyvinyl alcohol polyvinyl esters and TABLE IV ethers and acetals which contain sufiicient intralinear Grams COW OH Emulsion Q2332? Fog figzggf isge Plummed? CH2G tetmole groups to make them hydrophilic or water-soluble in character, hydrolyzed ethylene/vinylacetate copolymers, S

c g a: 3 agar agar, etc. Suitable colloids of these types are de- 3533 35 523, 1 33 20 2 scribed in the following U. S. patents: Jennings et a1.

and polymer. 2,397,864 and McQueen 2,397,866.

The examples illustrate that it is important to strike a proper concentration balance between the anti-plumming Example V agent and the protecting polymer if adequate inertization A Solution was prepared containing 05 g. of 1 pheny1 is to be obtained. This also alfords a means of regulating S-mercaptotetrazole as an anti-plumming agent dissolved the ratio, of mertlzed '5 Ponmemzed antl'plummmg in 15 ml. of ethyl alcohol containing methyl alcohol in agent ,whlch can be aPPhed In some cases to fog control the proportions, 100 parts 190 proof ethyl alcohol to 10 1! W111 PP F h' thfi abov? p that when parts pure methyl alcohol. This was added to a solution a PQlymerlc h fl g materlhl 15 used one P composed of 5 g. of diethylaminoethyl methacrylatc obtain good antl-plummlng effects with 1655 than a thlrd polymer made according to procedure B (48% polymer e amount of the f 'p 'h y by weight in toluene) dissolved in 25 ml. of toluene. q h' Whel1 afltl-plummlng agent 18 an effluent The solution obtained was dispersed in 150 ml. of disantl-foggmg materlal. such as the -p y p tilled water containing 2 g. of the sorbitan trioleate polytetrazolc used in the foregoing examples, the use of the oxyalkylene ether described in Example III as the dissmaller amounts permltted by the presence of the polypersing agent. Vigorous agitation in a blending mixer meric amino-nitrogen material is not disadvantageous, was employed for approximately three minutes to facilisince fogging can be controlled by the free agent present tate the formation of a uniform suspension. The .rewithout affecting other photographic characteristics such sultant dispersion was diluted to 500 ml. with distilled 86 as speed and contrast because of the small amounts re- .quired to minimize fog compared to the quantity needed to prevent plumming.

The invention is not limited to emulsions for photographic printing papers and similar papers, although that is the preferred aspect of the invention. The emulsions can be used in portrait and lithographic film and in seisrnographic recording materials, materials for recording spectographic line densities, etc.

An advantage of the invention is that it provides improved photographic elements. A further advantage is that it provides such elements which do not have adverse image densities or image color eifects upon drying of the developed elements. A still further advantage is that the anti-plumming and/or anti-bronzing agents do not leach out during processing. They can be used in smaller amounts thus reducing or eliminating any un favorable side effects, e. g., densitization. The above objects can be obtained in accordance with the invention in a simple manner and with relatively inexpensive materials. to divorce fog control from image color control. If the bronze image color is desired, fixing in plain sodium thiosulfate solution will minimize release of the anti-plumming agent and allow bronzing.

As many widely different embodiments of this invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not to be limited except as defined by the claims.

What is claimed is:

l. A photographic colloid-silver halide emulsion having dispersed therethrough particles of a polymeric amino-nitrogen containing organic material which is insoluble in water and 5% aqueous ammonia but soluble in 1% aqueous acetic acid and forms hard, resin-like films, said particles containing a sulfur-containing organic compound which has the property of preventing bronzeto plum-colored silver images upon the hot-drying of developed photographic silver images.

2. A photographic element comprising a paper sheet support bearing a photographic colloid-silver halide emulsion layer said emulsion having dispersed therethrough particles of a polymeric amino-nitrogen contain ing organic material which is insoluble in water and 5% aqueous ammonia but soluble in 1% aqueous acetic acid and forms hard, resin-like films, said particles containing In many cases this technique makes it possible Number a sulfur-containing organic compound which has the property of preventing bronzeto plum-colored silver images upon the hot-drying of developed photographic silver images.

3. A photographic gelatino silver halide emulsion having dispersed therethrough particles of a polymeric aminonitrogen containing organic resin insoluble in water and 5% aqueous ammonia but soluble in 1% aqueous acetic acid and forms hard resinous films said particles containing a S-mercapto-tetrazole having in the l-position a group taken from the class consisting a a hydrogen atom and a hydrocarbon radical.

4. A photographic gelatino silver halide emulsion having dispersed therethrough particles of polymeric diethylaminoethyl methacrylate containing a S-rnercaptotetrazole having in the 1-position a group taken from the class consisting of a hydrogen atom and a hydrocarbon radical, said polymeric diethylaminoethyl methacrylate being insoluble in water and 5% aqueous ammonia and soluble in 1% aqueous acetic acid and forming hard, resin-like films.

5. An emulsion as set forth in claim 4 where said tetrazole is 1-phenyl-5-mercaptotetrazole.

6. A photographic gelatino silver halide emulsion hav' ing dispersed therethrough particles of polymeric dimethylaminoethyl methacrylate containing a S-mercaptotetrazole having in the l-position a group taken from the class consisting of a hydrogen atom and a hydrocarbon radical, said polymeric diethylaminoethyl methacrylate being insoluble in water and 5% aqueous ammonia and soluble in 1% aqueous acetic acid and forming hard, resin-like films.

Barnes et a1 May 2, 1950 Lowe et al. Feb. l3, 195i FOREIGN PATENTS Country Date Great Britain Oct. 9, 1949 Number 

1. A PHOTOGRAPHIC COLLOID-SILVER HALIDE EMULSION HAVING DISPERSED THERETHROUGH PARTICLES OF A POLYMERIC AMINO-NITROGEN CONTAINING ORGANIC MATERIAL WHICH IS INSOLUBLE IN WATER AND 5% AQUEOUS AMMONIA BUT SOLUBLE IN 1% AQUEOUS ACETIC ACID AND FORMS HARD, RESIN-LIKE FILMS, SAID PARTICLES CONTAINING A SULFUR-CONTAINING ORGANIC COMPOUND WHICH HAS THE PROPERTY OF PREVENTING BRONZE- TO PLUM-COLORED SILVER IMAGES UPON THE HOT-DRYING OF DEVELOPED PHOTOGRAPHIC SILVER IMAGES. 